CN111349486A

CN111349486A - Low-sulfur diesel lubricity improver and preparation method thereof

Info

Publication number: CN111349486A
Application number: CN201811574820.6A
Authority: CN
Inventors: 王宜迪; 李澜鹏; 曹长海; 程瑾; 李秀峥
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2018-12-21
Filing date: 2018-12-21
Publication date: 2020-06-30
Anticipated expiration: 2038-12-21
Also published as: CN111349486B

Abstract

The invention relates to a low-sulfur diesel lubricity improver and a preparation method thereof, which is characterized in that unsaturated dihydric alcohol, tung oil biodiesel and ionic liquid are mixed according to a proportion, stirred and reacted at 40-60 ℃, cooled after the reaction, kept stand and layered, and the upper material is taken for reduced pressure distillation to obtain the lubricity improver product. According to the invention, unsaturated dihydric alcohol is used for modifying tung oil biodiesel in ionic liquid, so that the occurrence of cross-linking reaction is avoided, the prepared lubricity improver has the advantages of low blending ratio, good lubricity, good low-temperature fluidity and the like, and low-sulfur diesel can meet the national V lubricity standard and the condensation point requirement after blending.

Description

Low-sulfur diesel lubricity improver and preparation method thereof

Technical Field

The invention belongs to the technical field of biodiesel, and particularly relates to a low-sulfur diesel lubricity improver and a preparation method thereof.

Background

With the widespread use of diesel engines, the consumption of diesel fuel is increasing year by year. However, the large consumption of diesel fuel inevitably leads to further aggravation of the emission of harmful substances from vehicles. Since emissions have a serious impact on the ecological environment, human health and economic development, governments in various countries have successively enacted strict emissions regulations, limiting the harmful emissions of diesel vehicles. With the implementation of national standard V of diesel oil, the sulfur content of the diesel oil is reduced to below 10ppm, and the desulfurized diesel oil is implemented in domestic refineries. At present, sulfur reduction technologies such as hydrotreating, hydrocracking and the like are adopted in China, so that the sulfur content of fuel is greatly reduced, and the content of polar compounds in diesel oil is too low, so that the lubricity of the diesel oil is greatly reduced, the phenomenon of abrasion and damage of a large number of diesel oil pumps is caused, and the service life of the diesel oil pumps is shortened. The problem of lubricity of diesel oil is the first to appear in northern Europe, early nineties, the first low-sulfur diesel oil produced in Sweden has a sulfur content of less than 10ppm, aromatic hydrocarbons of less than 5%, a second sulfur content of less than 50ppm, and aromatic hydrocarbons of less than 20%, and the fraction of the diesel oil is basically kerosene fraction (95% distillation range is not more than 285 ℃), so that the natural lubricity of the diesel oil is reduced. When this diesel fuel was marketed, there began to be approximately 70 light duty diesel vehicles with fuel injection pump wear problems. In the popularization and use of low-sulfur diesel oil in the United states, a large number of lubrication problems are reported, particularly in winter low-cloud-point diesel oil, and when the sulfur content is lower than 100ppm, the problem of abrasion of an oil injection pump is already caused under the dual effects of the two factors due to poor lubricity and low viscosity of oil products. Therefore, improving the lubricity of low-sulfur diesel is one of the key problems in solving the wide-range popularization of low-sulfur diesel.

At present, a plurality of organizations develop the research of directly using vegetable oil as the low-sulfur diesel anti-wear agent. CS275894, EP605857 disclose the use of natural oils and fats such as rapeseed oil, sunflower oil, castor oil, etc. as anti-wear agents for low sulphur diesel oil directly. Although the vegetable oil has the advantages of easily available raw materials, low price and the like, the vegetable oil has relatively poor using effect, and has the defects of high viscosity, high condensation point and the like, so the vegetable oil is difficult to industrially apply.

The latest research result shows that the lubricity can be greatly improved by adding the biodiesel into the low-sulfur diesel, and the additional value of the biodiesel can be obviously improved. However, the lubricating effect of biodiesel can only be achieved at a relatively high addition level, and the addition level is usually more than 0.8% (volume fraction) so as to reduce the wear scar diameter of low-sulfur diesel to less than 460 μm (the enhancing effect of biodiesel on the lubricity of low-sulfur diesel [ J ], [ petroleum refining and chemical industry ], [ 2005, 36(7): 25-28), so that the economic efficiency of biodiesel as an additive is poor. In addition, the biodiesel contains a large amount of saturated fatty acid methyl ester, the condensation point is usually above-5 ℃, the use requirement of the low-sulfur diesel antiwear agent cannot be met, and the biodiesel cannot be suitable for cold regions. Therefore, the lubricity of biodiesel needs to be improved by a molecular modification means, and the blending ratio and the product solidifying point of the biodiesel in low-sulfur diesel are reduced.

CN1990835A discloses a preparation method of modified biodiesel capable of being used as a low-sulfur diesel antiwear agent, which greatly reduces the blending ratio, and the disclosed technical means is that biodiesel and polyalcohol undergo transesterification reaction, so as to obtain a modified biodiesel product. However, when the polyol is used as a raw material to perform ester exchange reaction, a polyester structure is easily formed, so that the condensation point of the product is too high, and the product performance cannot meet the requirement.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a low-sulfur diesel lubricity improver and a preparation method thereof. According to the invention, unsaturated dihydric alcohol is used for modifying tung oil biodiesel in ionic liquid, so that the occurrence of cross-linking reaction is avoided, the prepared lubricity improver has the advantages of low blending ratio, good lubricity, good low-temperature fluidity, low acid value and the like, and low-sulfur diesel can meet national V lubricity standard and condensation point requirements after blending.

The preparation method of the low-sulfur diesel lubricity improver provided by the invention comprises the following steps: mixing unsaturated dihydric alcohol, tung oil biodiesel and ionic liquid in proportion, stirring and reacting at 40-60 ℃ for a period of time, cooling after the reaction is finished, standing and layering, and carrying out reduced pressure distillation on the upper material to obtain the lubricity improver product.

In the present invention, the unsaturated diol is an unsaturated diol having not less than 3 carbon atoms, preferably 4 to 8 carbon atoms, and specifically, it is at least one of butenediol, pentenediol, hexenediol, heptenediol, and the like, preferably at least one of 2-butene-1, 4-diol, 1-butene-1, 4-diol, 2-pentene-1, 5-diol, 3-pentene-1, 5-diol, 2-hexene-1, 6-diol, 3-hexene-1, 6-diol, and the like, and more preferably 2-butene-1, 4-diol. The molar ratio of the unsaturated dihydric alcohol to the tung oil biodiesel is controlled to be 0.5:1-3:1, and preferably 0.8:1-2: 1.

In the invention, the tung oil biodiesel is fatty acid low carbon alcohol ester generated by the ester exchange reaction of tung oil and low carbon alcohol, the carbon atom number of the low carbon alcohol is preferably not more than 4, such as methanol, ethanol, propanol, butanol and the like, namely at least one of tung oil methyl ester, tung oil ethyl ester, tung oil propyl ester, tung oil butyl ester and the like, preferably tung oil methyl ester. The production process of biodiesel is various, and most commonly, a catalyst is used for catalyzing ester exchange reaction, namely natural oil and low-carbon alcohol are subjected to alcoholysis to obtain fatty acid low-carbon alcohol ester and glycerol under the action of the catalyst. The tung oil biodiesel used in the invention can be prepared by adopting conventional preparation methods in the field, such as an acid catalysis method, an alkali catalysis method, an enzyme catalysis method, a supercritical method and the like.

In the invention, the ionic liquid consists of imidazole cations and inorganic anions, wherein the imidazole cations are 1-butyl-3-methylimidazole cations, and the inorganic anions are one or more of tetrafluoroborate, hydrogen sulfate, dihydrogen phosphate and the like. The dosage of the ionic liquid is 0.1-2.0 times, preferably 0.2-1.0 times of the quality of the tung oil biodiesel.

In the invention, unsaturated dihydric alcohol, tung oil biodiesel and ionic liquid are mixed in proportion and stirred to react for 8-10h at 40-60 ℃.

In the invention, after the reaction is finished, the temperature is reduced to room temperature, then the mixture is stood for layering, and the lower layer material contains ionic liquid and can be recycled. And (3) taking the upper material to perform reduced pressure distillation, wherein the pressure of the reduced pressure distillation is 30-150Pa, preferably 65-120Pa, and the temperature is 180-220 ℃, preferably 195-205 ℃.

The low-sulfur diesel lubricity improver is prepared by the method. The prepared modifier is prepared by modifying tung oil biodiesel by unsaturated dihydric alcohol in ionic liquid, is a non-acid product, has an acid value of not more than 2mgKOH/g and a condensation point of not more than-24 ℃. The prepared lubricity improver has the advantages of low blending ratio, good lubricity, good low-temperature fluidity and the like, and the low-sulfur diesel oil can meet the national V lubricity standard and the condensation point requirement after blending.

The application of the lubricity improver for low-sulfur diesel oil prepared by the invention is used for improving the lubricity of the low-sulfur diesel oil, and when the dosage is 200-300ppm, the corrected wear scar diameter (60 ℃) of the low-sulfur diesel oil can be not more than 460 mu m. The low-sulfur diesel oil is diesel oil with the sulfur content less than 10ppm and the abrasive wear point diameter more than 580 mu m.

Compared with the existing lubricity improver, the invention has the following beneficial effects:

(1) according to the invention, by utilizing molecular structure modification, a polar group of unsaturated dihydric alcohol with a certain chain length is introduced into a tung oil biodiesel molecular chain and forms an aliphatic ring structure, so that a bilateral entanglement effect can be formed on an adsorption film, the entanglement density is effectively improved, the lubricating film is more compact, and the lubricity of low-sulfur diesel is greatly improved. Meanwhile, due to the introduction of an aliphatic ring structure, the intermolecular internal bonding effect is reduced, and the condensation point of the improver product can be reduced. The product performance of the improver prepared by the invention, such as the indexes of condensation point, flash point, metal content, low-temperature storage stability and the like, all meet the technical requirement of diesel antiwear agent (Q/SHCG 57-2014) of medium petrochemical industry.

(2) The modification reaction is carried out in the presence of the ionic liquid, the reaction of the tung oil biodiesel and the unsaturated dihydric alcohol can be catalyzed, the reaction temperature is reduced, the side reaction of ester exchange is effectively avoided, and no catalyst is required to be added.

(3) The product is a non-acid lubricity improver, has the characteristics of good lubricity, difficult emulsification, difficult precipitation at low temperature and the like, is particularly suitable for high-acid-value low-condensation diesel oil, cannot influence the acid value of the diesel oil, and avoids corrosion to a diesel engine.

(4) The invention uses tung oil biodiesel as a main raw material, and widens the raw material source of the low-sulfur diesel lubricity improver. In addition, the invention has the characteristics of simple and convenient process, easily obtained raw materials, low cost, easy industrial production and the like.

Drawings

FIG. 1 is a gas chromatogram of a methyl ester feedstock of tung oil.

FIG. 2 is a gas chromatogram of the improver product prepared in example 1.

Detailed Description

The low-sulfur diesel lubricity improver of the invention, the preparation method and the application effect thereof are further illustrated by the following examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.

The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.

In the invention, the acid value of the prepared improver for improving the lubricity of the low-sulfur diesel oil is determined according to a GB/T7304 method, the condensation point is determined according to a GB/T510 method, the lubricity is determined according to an SH/T0765 method (the lubricity refers to the diameter of the wear scar of the low-sulfur diesel oil after the improver is added), and the emulsifying property test is determined according to appendix C of a Q/SHCG57-2014 method.

The content of the conjugated octadecatrienoic acid ester containing conjugated double bonds in the tung oil biodiesel is detected according to a gas chromatography, wherein the chromatographic analysis conditions comprise an FID detector, the size of a chromatographic column is 100m × 0.25mm × 0.20.20 mu m, the temperature of a sample inlet is 260 ℃, the sample injection amount is 1 mu L, the split flow sample injection is carried out, the split flow ratio is 100: 1, the temperature rise program is that the temperature is started to be kept for 5 min at 140 ℃, the temperature is increased to 240 ℃ at 4 ℃/min and is kept for 4min, and the temperature of the detector is 260 ℃, and the content of the conjugated octadecatrienoic acid ester is detected to be B = 70.

Conversion rate of tung oil biodiesel A = (m)₁-m₂）/m₁× 100% where m is₁The feeding quality of the tung oil biodiesel is improved; m is₂The quality of the tung oil biodiesel is separated after the reaction.

The conversion rate of carbon-carbon conjugated double bonds of the tung oil biodiesel = A/B × 100%.

Example 1

Preparing tung oil methyl ester: adding 800g of tung oil, 160g of methanol and 8g of potassium hydroxide into a 2L high-pressure reaction kettle, stirring for reaction at the temperature of 60 ℃ for 20min, standing for layering after the reaction is finished, separating out 76.2g of lower-layer glycerin product, washing the upper-layer glycerin product for 3 times by using hot water at the temperature of 50 ℃, and distilling the washed product for 2 hours at the temperature of 2000Pa and 60 ℃ to obtain the tung oil methyl ester biodiesel.

176g of 2-butene-1, 4-diol, 500g of tung oil methyl ester and 250g of 1-butyl-3-methylimidazolium tetrafluoroborate are added into a reactor, the reaction temperature is controlled at 50 ℃, and the reaction is finished after the reaction is carried out for 9 hours at constant temperature under the stirring condition. When the system is cooled to room temperature and the reaction system is stood for layering, the lower layer is ionic liquid which can be recycled; and distilling the upper layer at the pressure of 65Pa and the temperature of 200 ℃ under reduced pressure for 2h to obtain the lubricity improver product. The conversion rate of the reaction molecules (the conversion rate of carbon-carbon conjugated double bonds of methyl tung oil) is calculated to be 64.2 percent. The detection shows that the condensation point is-26.5 ℃, and the water layer is not turbid in the demulsification test. As can be seen from fig. 1 and 2, a compound characteristic peak newly appeared at an outflow time of 14.05 min, demonstrating the formation of a lubricity improver.

Example 2

Adding 120g of 2-butene-1, 4-diol, 500g of tung oil methyl ester and 100g of 1-butyl-3-methylimidazole tetrafluoroborate into a reactor, controlling the reaction temperature to be 40 ℃, and reacting for 10 hours at constant temperature under the condition of stirring to finish the reaction. When the system is cooled to room temperature and the reaction system is stood for layering, the lower layer is ionic liquid which can be recycled; and distilling the upper layer at the pressure of 65Pa and the temperature of 200 ℃ under reduced pressure for 2h to obtain the lubricity improver product. The conversion rate of reaction molecules is 57.0 percent, the condensation point is-26.4 ℃, and a water layer is not turbid in a demulsification test.

Example 3

Adding 301g of 2-butene-1, 4-diol, 500g of tung oil methyl ester and 500g of 1-butyl-3-methylimidazolium tetrafluoroborate into a reactor, controlling the reaction temperature to be 60 ℃, and reacting for 8 hours at constant temperature under the condition of stirring to finish the reaction. When the system is cooled to room temperature and the reaction system is stood for layering, the lower layer is ionic liquid which can be recycled; and distilling the upper layer at the pressure of 65Pa and the temperature of 200 ℃ under reduced pressure for 2h to obtain the lubricity improver product. The conversion rate of reaction molecules is 64.7 percent, the condensation point is-26.7 ℃, and a water layer is not turbid in a demulsification test.

Example 4

176g of 2-butene-1, 4-diol, 500g of tung oil methyl ester and 250g of 1-butyl-3-methylimidazole hydrogen sulfate are added into a reactor, the reaction temperature is controlled at 50 ℃, and the reaction is finished after the reaction is carried out for 9 hours at constant temperature under the stirring condition. When the system is cooled to room temperature and the reaction system is stood for layering, the lower layer is ionic liquid which can be recycled; and distilling the upper layer at the pressure of 65Pa and the temperature of 200 ℃ under reduced pressure for 2h to obtain the lubricity improver product. The conversion rate of reaction molecules is 62.1 percent, the condensation point of a product is-26.5 ℃, and a water layer is not turbid in a demulsification test.

Example 5

176g of 2-butene-1, 4-diol, 500g of tung oil methyl ester and 250g of 1-butyl-3-methylimidazole dihydrogen phosphate are added into a reactor, the reaction temperature is controlled at 50 ℃, and the reaction is finished after the reaction is carried out for 9 hours at constant temperature under the stirring condition. When the system is cooled to room temperature and the reaction system is stood for layering, the lower layer is ionic liquid which can be recycled; and distilling the upper layer at the pressure of 65Pa and the temperature of 200 ℃ under reduced pressure for 2h to obtain the lubricity improver product. The reaction molecular conversion was 63.5%. The detection shows that the product has a condensation point of-26.3 ℃ and a water layer is not turbid in a demulsification test.

Example 6

204g of 2-pentene-1, 5-diol, 500g of tung oil methyl ester and 250g of 1-butyl-3-methylimidazolium tetrafluoroborate are added into a reactor, the reaction temperature is controlled at 50 ℃, and the reaction is finished after the reaction is carried out for 9 hours at constant temperature under the stirring condition. When the system is cooled to room temperature and the reaction system is stood for layering, the lower layer is ionic liquid which can be recycled; and distilling the upper layer at the pressure of 65Pa and the temperature of 200 ℃ under reduced pressure for 2h to obtain the lubricity improver product. The conversion rate of reaction molecules is 62.5 percent, the condensation point of a product is-26.8 ℃, and a water layer is not turbid in a demulsification test.

Example 7

232g of 3-hexene-1, 6-diol, 500g of tung oil methyl ester and 250g of 1-butyl-3-methylimidazole tetrafluoroborate are added into a reactor, the reaction temperature is controlled at 50 ℃, and the reaction is finished after the reaction is carried out for 9 hours at constant temperature under the stirring condition. When the system is cooled to room temperature and the reaction system is stood for layering, the lower layer is ionic liquid which can be recycled; and distilling the upper layer at the pressure of 65Pa and the temperature of 200 ℃ under reduced pressure for 2h to obtain the lubricity improver product. The reaction molecular conversion was 60.5%. The product has a condensation point of-27.0 ℃, and a water layer is not turbid in a demulsification test.

Example 8

232g of 2-hexene-1, 6-diol, 500g of tung oil methyl ester and 250g of 1-butyl-3-methylimidazole tetrafluoroborate are added into a reactor, the reaction temperature is controlled at 50 ℃, and the reaction is finished after the reaction is carried out for 9 hours at constant temperature under the stirring condition. When the system is cooled to room temperature and the reaction system is stood for layering, the lower layer is ionic liquid which can be recycled; and distilling the upper layer at the pressure of 65Pa and the temperature of 200 ℃ under reduced pressure for 2h to obtain the lubricity improver product. The conversion rate of reaction molecules is 60.1 percent, the condensation point of a product is-26.9 ℃, and a water layer is not turbid in a demulsification test.

Example 9

Adding 800g of tung oil, 230g of ethanol and 8g of potassium hydroxide into a 2L high-pressure reaction kettle, stirring for reaction at the temperature of 60 ℃ for 20min, standing for layering after the reaction is finished, separating 74.8g of lower-layer glycerol product, washing the upper-layer product for 3 times by using hot water at the temperature of 50 ℃, and distilling the washed product for 2 hours at the temperature of 2000Pa and 60 ℃ to obtain the tung oil ethyl ester biodiesel.

The other preparation processes and operation conditions are the same as those of the example 1, but the difference is that the tung oil methyl ester is replaced by the tung oil ethyl ester, the reaction molecular conversion rate is 59.7 percent, the condensation point is-26.9 ℃, and a water layer is not turbid in a demulsification test.

Example 10

Adding 800g of tung oil, 320g of n-propanol and 8g of potassium hydroxide into a 2L high-pressure reaction kettle, stirring for reaction at the temperature of 60 ℃ for 20min, standing for layering after the reaction is finished, separating 72.4g of lower-layer glycerol product, washing the upper-layer glycerol product for 3 times by using 50 ℃ hot water, and distilling the washed product at the temperature of 2000Pa and 60 ℃ for 2h to obtain the tung oil propyl ester biodiesel.

The other preparation processes and operation conditions are the same as those of the example 1, but the difference is that the tung oil methyl ester is replaced by the tung oil propyl ester, the conversion rate of reaction molecules is 58.0 percent, the condensation point is-27.5 ℃, and a water layer is not turbid in a demulsification test.

Example 11

Adding 800g of tung oil, 400g of n-butanol and 8g of potassium hydroxide into a 2L high-pressure reaction kettle, stirring for reaction at the temperature of 60 ℃ for 20min, standing for layering after the reaction is finished, separating 70.4g of lower-layer glycerin product, washing the upper-layer glycerin product for 3 times by using 50 ℃ hot water, and distilling the washed product for 2 hours at the temperature of 2000Pa and 60 ℃ to obtain the tung oil butyl ester biodiesel.

The other preparation processes and operation conditions are the same as those of the example 1, but the difference is that the tung oil butyl ester is adopted to replace tung oil methyl ester, the reaction molecular conversion rate is 56.8 percent, the condensation point is-28.3 ℃, and a water layer is not turbid in a demulsification test.

Comparative example 1

The preparation process and the operation conditions are the same as those of the example 1, except that no ionic liquid is added, the conversion rate of reaction molecules is less than 0.5 percent, and a lubricity improver product cannot be synthesized.

Comparative example 2

The preparation process and the operating conditions were the same as in example 1, except thatNThe conversion rate of reaction molecules of the-ethyl pyridine tetrafluoroborate ionic liquid is less than 0.5 percent, and a lubricity improver product cannot be synthesized.

Comparative example 3

The preparation process and operating conditions were the same as in example 1, except that other biodiesel, such as soybean oil biodiesel, cottonseed oil biodiesel, rapeseed oil biodiesel, castor oil biodiesel, corn oil biodiesel, etc., was used. Because the biodiesel does not contain conjugated double bonds, the system does not react, and the product cannot be obtained.

Comparative example 4

The preparation process and the operation conditions are the same as those in the example 1, but the preparation process and the operation conditions are different in that unsaturated monohydric alcohol is adopted, such as any one of 2-propenyl alcohol, 3-n-butenyl alcohol and 4-n-pentenol, and because only monohydric alcohol is introduced into tung oil biodiesel for modification, the lubricating effect of the product is poor, and the technical index of the grinding mark diameter specified in the technical requirement of diesel antiwear agent (Q/SHCG 57-2014) is not met.

Test example 1

The low-sulfur diesel oil used in the test examples of the invention is hydrofined diesel oil with the sulfur content of less than 10ppm and the wear-leveling diameter of more than 580 μm, and the specific properties of the low-sulfur diesel oil are shown in Table 1.

TABLE 1 Main physical Properties of two low-sulfur diesel fuels

The lubricity improver prepared by the invention is added into the low-sulfur diesel oil for product performance test. The test results are shown in tables 2 and 3.

TABLE 2

As can be seen from Table 2, the lubricating effect of the directly adopted tung oil biodiesel on low-sulfur diesel oil is poor, when 800ppm of the lubricating agent is added, the lubricating property of the low-sulfur diesel oil does not meet the lubricating property requirement of national V diesel oil, and the modifier is separated out at the temperature of minus 20 ℃. After the modification by the method, the lubricity of the product on low-sulfur diesel oil is remarkably improved, and when the addition amount is reduced to 200ppm, the blended low-sulfur diesel oil can meet the requirement of national V diesel oil lubricity (the abrasive wear pattern diameter is no more than 460 mu m), and no precipitation exists at the temperature of minus 20 ℃. The prepared novel lubricity improver has an obvious lubricating effect, and is low in blending ratio and condensation point.

TABLE 3

As can be seen from Table 3, the lubricating effect of the directly adopted tung oil biodiesel on low-sulfur diesel oil is poor, when 800ppm of the lubricating oil is added, the lubricating property of the low-sulfur diesel oil does not meet the lubricating property requirement of national V diesel oil, and the improver is separated out at-30 ℃ and does not meet the use requirement. After the modification by the method, the lubricity of the product on low-sulfur diesel oil is remarkably improved, when the addition amount is reduced to 300ppm, the blended low-sulfur diesel oil can meet the requirement of national V diesel oil lubricity (the abrasive wear spot diameter is no more than 460 mu m), and particularly after the blended low-sulfur diesel oil is blended with the low-sulfur diesel oil at the low temperature of-30 ℃, no improver is separated out, and the quality of the diesel oil is not influenced. The novel lubricity improver prepared by the invention has obvious lubricating effect, low blending ratio and low condensation point.

Claims

1. The preparation method of the low-sulfur diesel lubricity improver is characterized by comprising the following steps of: mixing unsaturated dihydric alcohol, tung oil biodiesel and ionic liquid in proportion, stirring and reacting at 40-60 ℃ for a period of time, cooling after the reaction is finished, standing and layering, and carrying out reduced pressure distillation on the upper material to obtain the lubricity improver product.

2. The method of claim 1, wherein: the unsaturated diol has a carbon number of not less than 3, preferably 4 to 8.

3. The method of claim 2, wherein: the unsaturated diol is at least one of butylene diol, pentylene diol, hexylene diol and heptylene diol.

4. The method of claim 3, wherein: the unsaturated dihydric alcohol is at least one of 2-butene-1, 4-diol, 1-butene-1, 4-diol, 2-pentene-1, 5-diol, 3-pentene-1, 5-diol, 2-hexene-1, 6-diol and 3-hexene-1, 6-diol.

5. The method of claim 1, 2, 3 or 4, wherein: the molar ratio of the unsaturated dihydric alcohol to the tung oil biodiesel is controlled to be 0.5:1-3:1, and preferably 0.8:1-2: 1.

6. The method of claim 1, wherein: the tung oil biodiesel is fatty acid low-carbon alcohol ester generated by the ester exchange reaction of tung oil and low-carbon alcohol, and preferably at least one of tung oil methyl ester, tung oil ethyl ester, tung oil propyl ester and tung oil butyl ester.

7. The method of claim 1, wherein: the ionic liquid consists of imidazole cations and inorganic anions, wherein the imidazole cations are 1-butyl-3-methylimidazole cations, and the inorganic anions are one or more of tetrafluoroborate, hydrogen sulfate, dihydrogen phosphate and the like.

8. The method according to claim 1 or 7, characterized in that: the dosage of the ionic liquid is 0.1-2.0 times, preferably 0.2-1.0 times of the quality of the tung oil biodiesel.

9. The method of claim 1, wherein: mixing unsaturated dihydric alcohol, tung oil biodiesel and ionic liquid in proportion, and stirring at 40-60 deg.C for 8-10 hr.

10. The method of claim 1, wherein: the pressure of the reduced pressure distillation is 30-150Pa, preferably 65-120Pa, and the temperature is 180-220 ℃, preferably 195-205 ℃.

11. A low sulfur diesel lubricity improver prepared by the process of any one of claims 1 to 10.

12. The use of a lubricity improver according to claim 11, characterized in that: the lubricating agent is used for improving the lubricity of the low-sulfur diesel oil, when the dosage is 200-300ppm, the low-sulfur diesel oil meets the national V lubricity standard, and the corrected wear scar diameter is not more than 460 mu m.

13. Use according to claim 12, characterized in that: the low-sulfur diesel oil is diesel oil with the sulfur content less than 10ppm and the abrasive wear point diameter more than 580 mu m.